CN104583314B - Polyester and resin composition and the polyester film of use said composition - Google Patents

Polyester and resin composition and the polyester film of use said composition Download PDF

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CN104583314B
CN104583314B CN201380045267.6A CN201380045267A CN104583314B CN 104583314 B CN104583314 B CN 104583314B CN 201380045267 A CN201380045267 A CN 201380045267A CN 104583314 B CN104583314 B CN 104583314B
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polyester
silicon dioxide
resin composition
film
dioxide granule
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CN104583314A (en
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郑裕仁
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Kolon Corp
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Kolon Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/2438—Coated

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The present invention relates to a kind of polyester and resin composition and use the polyester film of said composition.More specifically, the present invention relates to a kind of polyester and resin composition and use the polyester film of said composition, wherein, described polyester and resin composition comprises polyester resin and is coated with the silicon dioxide granule of metallic compound, it is therefore prevented from the internal flaw caused by particle accumulation, and achieve the transparency of the surface property of improvement, low haze and improvement, so that this polyester and resin composition can be suitable as blooming and electronic material basement membrane.

Description

Polyester and resin composition and the polyester film of use said composition
Technical field
The present invention relates to a kind of polyester and resin composition and use the polyester film of said composition, more specifically, relating to one Planting polyester and resin composition and use the polyester film of said composition, described polyester and resin composition comprises polyester resin and is coated with The silicon dioxide granule of metallic compound is to prevent the internal flaw caused because of particle accumulation, and has the film superficiality of excellence Energy, low haze and the transparency of improvement, thus it is applicable to electronic material stripping film and blooming.
Background technology
Generally, polyester, particularly polyethylene terephthalate (hereinafter referred to as PET) are owing to having the heat-resisting of excellence Property, mechanical strength, the transparency and chemical resistance etc. are utilized as film, fiber, container or bottle and mechanically and electrically subassembly. Additionally, polyester is more less expensive than other high functionality resin so that its purposes and usage amount progressively and constantly increase.Especially It is that the polyester film that prior art produces has been widely used in multiple fields, such as magnetic recording media, various packaging, product Product protection, electronic material, interlayer, window and the basement membrane of stripping film, and in the last few years, along with the various electricity for display The exploitation of sub-product, the commercially available extension centered by electronic material basement membrane and blooming.
In polyester film has the large temperature range from low temperature to high temperature, excellent physical property stability is polymerized with other Resin compares the chemical resistance of excellence, good mechanical strength, good surface property, good thickness evenness and right Various application or the excellent adaptability of processing conditions so that it can be used in condenser, film, label, pressure sensitive adhesive tape, dicoration Laminated product, conveyer belt, polarizer and ceramic sheet material etc..Additionally, in order to meet the most at a high speed and the trend of automatization, for poly- The demand of ester film is just growing.
The polyester film used in field of display have been used for carrying out multiple tracks technique (such as by off-line be coated with hard Coating process) for the touch panel basement membrane in liquid crystal indicator, for Plasmia indicating panel (PDP) film Film, for the basement membrane of diffusion sheet, prismatic lens or the prism protecting film etc. that are included in back light unit, and for anti-reflective coating The basement membrane of layer with prevent by ambient cause dizzy etc..
The above-mentioned basement membrane used in field of display needs to have such as to process navigability, scoring resistance, printing opacity Property and the various features such as the brightness of excellence and acutance, it is therefore desirable to a kind of inside making deterioration excellent transparency and flatness The technology that defect and surface defect minimize.Additionally, in the case of described film is used as stripping film, will in last handling process This film pastes on electronic material and separates, it is therefore desirable to control the relatively low surface roughness of basement membrane and uniform surface Roughness and defect.
In this article, defined defect in the present invention, wherein internal flaw refers to be present in polyester resin and tool Having different refractive indexs to cause reflection and the scattering of light, so that the factor of the transparency deterioration of polyester resin, this defect can To be caused by inorganic metal, foreign substance, particles aggregate and carbide.Additionally, surface defect refers to be present in polyester film surface Above cause the reflection of light and the factor of scattering, and the such as problem such as scratch or rough surface in last handling process.
In order to be used as electronic material stripping film and basement membrane in field of display, it is single-minded that described film should have optics Property also needs multiple requirement.When the flatness (its be film required for one of performance) of film is poor, in the preparation of basement membrane In journey, tension force is uneven and cause sliding phenomenon so that occur scratch defects etc. on the surface of film, and coated in post processing Coated weight in journey is uneven, thus produces topical application defect, so that the value of product declines.
Additionally, when scratch occurs on basement membrane, for having the part of scratch, be likely to be due to over transparent conductive layer Uneven coating and produce black speck (its for a kind of electrical defect), or in the aftertreatment technologys such as such as hard coating it may happen that Uneven coating, it is therefore desirable to the performance of scratch resistant.
Using normal polyester resin to prepare in the technique of film, making by the amorphous sheet of extrusion die molding through multiple Roller, stretches and is wound in film roll, then cutting, herein, in order to through multiple rollers or be wound, it should make film have suitable When roughness.To this end, generally the catalyst added when polymeric polyester is combined with polyester components or phosphorus component, and Utilize inside deposition particle polyester dissolubility declined and generate, such that it is able to provide roughness.But, internal heavy using In the case of long-pending particle, described particle is present in polyester resin the effect playing internal flaw, it might even be possible in high-quality Blooming plays the effect of critical defect.Additionally, in the case of using external inorganic or organic filler, processing transmission performance (process passing performance), such as, the surface defect of the surface scratches of such as film, the film being wound around by roller Wrinkle resistance and the most received film end face (excluded end surface of the film) increase.Meanwhile, film The transparency may deteriorate, and the deviation between high surface roughness and low surface roughness may increase and make flatness bad Change.
Korean Patent Publication is announced No.10-2004-0062245 (patent documentation 1) and is disclosed a kind of biaxially-oriented polyester Film, wherein adds the porous spherical silicon dioxide with bigger oil absorption；But, the phase between polyester resin with silicon dioxide Capacitive is undesirable and causes space, so that the transparency deterioration of film.
Therefore, to the excellent compatibility and particle with polyester resin in resin not coagulation and reduce internal flaw so that The flatness of film and the polyester and resin composition that scoring resistance is excellent, surface roughness is low and transparency is high are studied.
[prior art literature]
(patent documentation 1) Korean Patent Publication announces No.10-2004-0062245 (on July 7th, 2004)
Summary of the invention
Technical problem
It is an object of the present invention to provide a kind of polyester and resin composition, in the composition, polyester resin and polyester The internal flaw of film reduces, and flatness is excellent, and surface roughness is relatively low, and roughness deviation is less, there is not surface scratches and different Often defect, mist degree is relatively low, and the transparency is excellent.
It is also an object of the invention that by use described polyester and resin composition, it is provided that one have low slightly Rugosity and the polyester film of the high grade of transparency, this polyester film is applicable to electronic material stripping film or blooming.
Furthermore it is also an object that provide one prepare polyester and resin composition and have low roughness and The method of the polyester film of the high grade of transparency.
Technical scheme
At a total aspect, the present invention provides a kind of polyester and resin composition, comprises: polyester resin and be coated with metal The silicon dioxide granule of compound, wherein, described silicon dioxide granule meets Equation 1 below, and this silicon dioxide granule Any three points relative to PmaxAngle of circumference be 85 to 90 degree:
0.9≤Pmin/Pmax≤ 1.0 [equatioies 1]
(in equation 1, PminFor the minimum diameter of described silicon dioxide granule, PmaxMaximum for this silicon dioxide granule Diameter.)
The particle mean size of the described silicon dioxide granule being coated with metallic compound can be 0.1 to 1.0 μm, described metal The coating thickness of compound can be 0.01 to 0.1 μm, and described in be coated with the silicon dioxide granule of metallic compound poly- Content in ester resin composition can be 0.001 to 0.3wt%.
90% cumulative particle sizes (d90) of the described silicon dioxide granule being coated with metallic compound can be 0.3 to 0.8 μ M, maximum particle size (dmax) can be 0.4 to 1.0 μm, and described metallic compound can be selected from aluminium oxide, zirconium oxide, two Titanium oxide, stannum oxide and zinc oxide any one or two or more.
Described polyester and resin composition can also comprise catalyst, electrostatic pinning agent (electrostatic pinning Agent) and phosphorus compound, wherein, described catalyst, electrostatic pinning agent and phosphorus compound can meet equation 2 below extremely 5:
50≤MeC≤ 200 [equatioies 2]
30≤MeP≤ 200 [equatioies 3]
100≤MeC+MeP≤ 300 [equatioies 4]
30≤P≤100 [equation 5]
(in equation 2, MeCFor the metal that contains in described catalyst relative to the content of total polyester and resin composition (ppm), in equation 3, MePFor the metal that contains in described electrostatic pinning agent relative to the content of total polyester and resin composition (ppm), in equation 4, MeC+MePFor the metal of described catalyst and electrostatic pinning agent relative to total polyester and resin composition Total content (ppm), in equation 5, P is the phosphorus that contains in the phosphorus compound content relative to total polyester and resin composition (ppm)。)
In the area of 448 μ m 336 μm, the number of defects more than a size of 1.5 μm can be less than 7.
In another general aspect, the present invention provides a kind of by using above-mentioned polyester and resin composition, then melted crowded Go out and stretch and the polyester film prepared.
Described polyester film can contain the silicon dioxide granule being coated with metallic compound of 0.001 to 0.3wt%, and Can have the mist degree less than 5% and the surface roughness (Ra) less than 15nm.
In another general aspect, the present invention provides a kind of method preparing polyester and resin composition, including: poly-in synthesis During ester resin, mixing is coated with the silicon dioxide granule of metallic compound, and wherein, described silicon dioxide granule meets following etc. Formula 1, and any three points of this silicon dioxide granule are relative to PmaxAngle of circumference be 85 to 90 degree:
0.9≤Pmin/Pmax≤ 1.0 [equatioies 1]
(in equation 1, PminFor the minimum diameter of described silicon dioxide granule, PmaxMaximum for this silicon dioxide granule Diameter.)
When mixing silicon dioxide granule, the described silicon dioxide granule being coated with metallic compound can be dispersed in two In alcohol and be mixed into slurry form.
Beneficial effect
According to the present invention, described polyester and resin composition can comprise the preparing spherical SiO 2 being coated with metallic compound, Thus particle dispersibility in resin can be improved and reduce the frictional force on film surface, thus reduce film when preparing film Internal flaw.
Additionally, when preparing polyester resin, resin comprises the content of metal and phosphorus according to catalyst, electrostatic pinning agent It is adjusted with the content of phosphorus compound, thus defect present in resin can be reduced, and can be coated with described The preparing spherical SiO 2 of metallic compound improves surface property together.
It addition, the excellent compatibility between described polyester resin and the preparing spherical SiO 2 being coated with metallic compound, because of And make flatness and processing navigability the most excellent, and can be formed and there is no surface scratches or the film of abnormal defect.
Therefore, it can prepare the transparency and the film of surface property with excellence.
Accompanying drawing explanation
Fig. 1 is the general of the maximum gauge of the silicon dioxide granule being coated with metallic compound of the explanation present invention and angle of circumference The property read schematic diagram.
Detailed description of the invention
Hereinafter, by for the method preparing polyester and resin composition and film, preferred exemplary enforcement is described in detail Scheme and assessment factor.Can specifically understand the present invention by following illustrative embodiment, provide these exemplary realities The scheme of executing is as an example and is not intended to limit the protection domain limited by claims of the present invention.
It is desirable to provide a kind of polyester and resin composition and use said composition there is low roughness and height is saturating The polyester film of lightness, described polyester and resin composition comprises the preparing spherical SiO 2 being coated with metallic compound to improve particle Dispersibility also reduces the skin-friction force of film, thus reduces the defect in film when preparing film.
The inventors discovered that, the organic or inorganic particle added as anticaking agent in the polymerization of polyester resin can be in system Internal flaw and surface defect is caused during standby polyester film.Additionally, the inventors discovered that, due to anticaking agent phase in polyester resin Assemble mutually, therefore bad with the compatibility of polyester resin, thus cause space when stretched film, inside and table are played in these spaces The effect of planar defect.And, the inventors discovered that, granularity increase makes the surface roughness of film improve, due to roughness not Equilibrium, cause roughness deviation increase and make roughness descent, thus can not be evenly coated with in post processing coating solution and Slurry.
Therefore, the inventors discovered that, in optical property and the superficiality of the film using described polyester and resin composition to prepare In the range of deteriorating, i.e. mist degree be less than 5%, average surface roughness Ra be below 15nm scope in, make With preparing spherical SiO 2 (being coated with the preparing spherical SiO 2 that metallic compound and sphericity are close to 1), one is thus provided to have The optics polyester and resin composition of the internal flaw, low haze and the excellent surface performance that reduce, thus complete the present invention.
Hereinafter, will be described in detail the present invention.
The polyester and resin composition of the present invention can comprise polyester resin and be coated with the silicon dioxide grain of metallic compound Son.
Even if in the silicon dioxide granule with same average particle size, by coating and polyester resin, there is high-affinity Metallic compound, be coated on silicon dioxide granule and can have with the metallic compound of the compatibility of polyester resin to improve The significantly excellent transparency.Described metallic compound can unrestrictedly use, particularly, selected from zirconium oxide, aluminium oxide, dioxy Change titanium, stannum oxide and zinc oxide any one or two or more be all effective for improving with the affinity of polyester resin.
Described metallic compound is preferably with 0.01 to 0.1 μm, and the thickness of more preferably 0.05 to 0.1 μm is coated in titanium dioxide On the surface of silicon.In the case of with above-mentioned thickness coating metallic compound, the compatibility with polyester resin can be effectively improved, And in the case of using described metallic compound to prepare film, space can be suppressed to improve transparency and reduce mist degree.
In the case of the coating thickness of metallic compound is less than 0.01 μm, coating layer thickness is the thinnest, thus is difficult to improve Affinity with polyester resin；And in the case of coating thickness is more than 0.1 μm, the overall size of particle increases and increases surface Roughness, so that flatness may deteriorate, and is likely to result in the dispersion of light and makes transparency decline.
The silicon dioxide granule being preferably coated with metallic compound meets Equation 1 below, and by the phase shown in Fig. 1 For maximum gauge PmaxThe angle of circumference (A1-A3) of any three points be 85 to 90 degree:
0.9≤Pmin/Pmax≤ 1.0 [equatioies 1]
(in equation 1, PminFor the minimum diameter of described silicon dioxide granule, PmaxMaximum for this silicon dioxide granule Diameter.)
The full-size of the described silicon dioxide granule being coated with metallic compound and spherical form can be by scanning electricity Sub-microscope (SEM) irradiates to be measured, and at the minimum diameter (P defined in above-mentioned equation 1min) and maximum gauge (Pmax) it Ratio is 0.9 to 1.0 so that this silicon dioxide granule is substantially spherical, and such shape is effective.It is being coated with metallization The silicon dioxide granule of compound be spherical in the case of, it is possible to use the amount of its minimum and notable and the grasping of holding film effectively Vertical property.
In the present invention, each particle during " minimum diameter " refers to more than 20 particles based on SEM photograph is Minor diameter, " maximum gauge " refers to the maximum gauge of each particle in more than 20 particles based on SEM photograph.
The particle mean size of the described silicon dioxide granule being coated with metallic compound can be 0.1 to 1.0 μm, swashs using Optical diffraction-scattering scheme, by using particle size distribution analysis instrument to measure in the case of granularity, when tiring out the volume of small grain size Timing, meeting the granularity i.e. d90 value corresponding to 90% is 0.3 to 0.8 μm, and maximum particle size dmaxValue be 0.4 to 1.0 μm be to have Effect.
Being coated with the particle mean size of silicon dioxide granule of metallic compound less than in the case of 0.1 μm, the transparency is relatively For excellence, but processing characteristics declines and particle reassembles into bigger particle, thus there may be defect when preparing film；And Particle mean size is more than in the case of 1.0 μm, and processing characteristics is improved, but surface roughness increases and surface irregularity, thus Surface property may deteriorate, and be likely to result in scattering of light and make transparency deteriorate.Additionally, be coated with the dioxy of metallic compound SiClx particle exists as surface defect so that light transmittance declines and forms space, and thus, in drawing process, film ruptures And make the productivity of polyester film reduce.
Additionally, in the polyester film using the polyester and resin composition with low roughness and the high grade of transparency, described coating The content having the silicon dioxide granule of metallic compound can be 0.001 to 0.3wt%.There is the polyester film of above-mentioned scope content Not only there is transparency and the flatness of excellence, and there is the processing characteristics of excellence, i.e. navigability, thus on the surface of film On will not produce scratch or abnormal defect.
It is being coated with the content of silicon dioxide granule of metallic compound less than in the case of 0.001wt%, is improving smooth The effect of degree and processing characteristics is less obvious, thus may produce scratch and abnormal defect in a large number when preparing film；And described The content of silicon dioxide granule is more than in the case of 0.3wt%, and when preparing film, a large amount of particles may mutually be assembled and cause table Planar defect, makes surface roughness increase, and transparency may deteriorate, and mist degree may be higher.
In the present invention, polyester resin can be to pass through esterification or ester exchange reaction, such as dicarboxylic acids or its ester Derivant and glycol or the melt polycondensation reaction of derivant of its ester and the conventional polyester homopolymer prepared or conventional polyester altogether Polymers, it is highly preferred that described polyester resin can be the polyester tree prepared by the polymerization of metallic catalyst and electrostatic pinning agent Fat.
As described dicarboxylic acids or the derivant of its ester, can mainly use p-phthalic acid or its Arrcostab or phenylester Deng, but one part can use such as bifunctional carboxylic acid's such as isophthalic acid, oxidation ethoxybenzoic acid (oxyethoxy Benzoic acid), adipic acid, decanedioic acid, 5-sulfoisophthalic acid sodium or their ester-formin derivant substitute use. Additionally, the derivant of described glycol or its ester typically ethylene glycol, but one part can with such as 1,3-PD, three Methylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,4 cyclohexane dimethanol, neopentyl glycol, 1,4-dual oxide ethyoxyl Benzene (Isosorbide-5-Nitrae-bisoxyethoxybenzene), bis-phenol, Polyethylene Glycol substitute use, and can use a small amount of simple function Compound or trifunctional compound.
In the present invention, described catalyst is not limited, as long as this catalyst is in the polycondensation process of polyester Use.More preferably, it is possible to use the such as metallic catalyst such as stannum or antimony, antimonial, germanium can more specifically be used Compound or titanium compound etc..
The content of the metal in described catalyst can meet equation 2 below, it is highly preferred that be present in metallic catalyst In metal content in total polyester and resin composition can be 50 to 150ppm.
50≤MeC≤ 200 [equatioies 2]
(in equation 2, MeCFor the metal that contains in described catalyst relative to the content of total polyester and resin composition (ppm)。)
There is the content of metal in the catalyst less than in the case of 50ppm, by the effect using catalyst to obtain less Substantially；And in the case of tenor is more than 200ppm, metal may be made to deposit from resin due to metal excess, Or it is likely to be formed complex and causes internal flaw.
Electrostatic pinning agent in the present invention is not limited, as long as this electrostatic pinning agent is for conventional, more preferably Ground, it is possible to use bivalent metallic compound, More specifically, because bigger electrostatic activity and alkali metal chemical combination can be used Thing, alkaline earth metal compound, manganese compound, cobalt compound and zinc compound, as its instantiation, it is possible to use magnesium acetate, Sodium acetate, calcium acetate, Quilonorm (SKB), calcium phosphate, magnesium oxide, magnesium hydroxide, magnesium alkoxide, manganese acetate and zinc acetate, it is possible to will wherein One or more are used in mixed way.
The content being present in the metal in described electrostatic pinning agent can meet equation 3 below, it is highly preferred that total Content in polyester and resin composition can be 50 to 150ppm.
30≤MeP≤ 200 [equatioies 3]
(in equation 3, MePFor the metal that contains in described electrostatic pinning agent relative to total polyester and resin composition Content (ppm).)
The total content of the metal in electrostatic pinning agent within the above range in the case of, can prepare so that navigability Raising, the film that internal flaw reduces and mist degree is relatively low.Meanwhile, in the case of the usage amount of electrostatic pinning agent is less than 30ppm, can Can cannot obtain and improve the effect of navigability because using electrostatic pinning agent, thus when preparing film, navigability may be bad Change and cause defect；And in the case of the usage amount of electrostatic pinning agent is more than 200ppm, is likely to be due to metal excess and is formed poly- Collection or complex and cause internal flaw.
Additionally, the total content of the metal contained in described catalyst and electrostatic pinning agent can meet equation 4 below.
100≤MeC+MeP≤ 300 [equatioies 4]
(in equation 4, MeC+MePFor the metal of described catalyst and electrostatic pinning agent relative to total polyester resin composition The total content (ppm) of thing.)
In the case of the total content of metal is less than 100ppm, uses the effect of catalyst and improve the effect of navigability May be less obvious；And in the case of the total content of metal is more than 300ppm, due to metal excess, metal may be from resin Deposit or be likely to be formed complex and cause internal flaw, thus preferably make the total content of metal be included in above-mentioned scope Content within.
The present invention can also comprise phosphorus compound to provide heat stability, and wherein this phosphorus compound can be tripotassium phosphate Ester, triethyl phosphate, and can be phosphoric acid when needing.Described phosphorus compound may be provided for making pinning performance and heat stability Obtain the effect of improvement together.
The content being present in the phosphorus in described phosphorus compound can meet equation below 5, it is highly preferred that at total polyester Content in resin combination can be 30 to 60ppm.
30≤P≤100 [equation 5]
(in equation 5, P is the phosphorus that contains in the described phosphorus compound content relative to total polyester and resin composition (ppm)。)
It is highly preferred that in the case of meeting melted resistor satisfied 2 to the 8M Ω of equation 6 and prepared resin, permissible Make to be minimized by the internal flaw of metallic catalyst deposition, and the film with low haze can be prepared.
0.5≤[P]/[MeP]≤1.5 [equation 6]
(in equation 6, [P] is the equivalent of the phosphorus in described phosphorus compound, [MeP] it is the metal compound as pinning agent The total yield sum of the metal in thing.)
Equation 6 means the equivalent proportion between the anion produced by phosphorus and the cation produced by metal, wherein, is applied to Electric current on casting drum usually negative (-), thus described polyester and resin composition can be just (+) to provide pinning performance, for This, when being introduced, as previously discussed, to phosphorus compound, equivalent proportion can be controlled and make said composition be just (+).It is less than in equivalent proportion 0.5 or melted resistance less than in the case of 2, can improve navigability and processing characteristics, but the excess metal of electrostatic pinning agent Internal flaw may be caused, and the color of fluoropolymer resin may turn yellow；And be more than more than 1.5 or melted resistance in equivalent proportion In the case of 8, electrostatic pinning performance is not enough, thus is difficult to make the manipulation speed normalization of film, and productivity may deteriorate, processing characteristics May decline, it is possible to create the surface scratches such as such as pinning scratch, and open defect may be caused.
Additionally, the compositions of the present invention can also comprise the additive of routine, it is selected from two grades of fire retardants, pigment or dye The reinforcing agents such as material, such as glass fibre, filler, heat-resistant agent, shock absorbent, for improving the fluorescent whitening agent of color and contain There are any one or two or more color perfecting agent of the germanium compound of germanium oxide.
In the present invention, the silicon dioxide granule being coated with metallic compound can mix when synthesizing polyester resin Close, more specifically, the derivant of the derivant of dicarboxylic acids or its ester with glycol or its ester is mutually mixed and prepares slurry, so After carry out direct esterification reaction and prepare lower-molecular substance (oligomer of low-molecular-weight)；Electrostatic agent and phosphorus compound being added should In lower-molecular substance, be added thereto to other additive, and with the dioxy being coated with metallic compound being dispersed in glycol SiClx mix particles, then carries out polycondensation reaction and prepares polyester and resin composition.
More specifically, in order to prepare the polyester film with excellent surface performance and the transparency in the present invention, first make With high speed agitator, described preparing spherical SiO 2 particles is mixed with glycol and prepares slurry, then filter, classification or grind with For preparing polyester film.The glycol in (C2～C10) glycol can be used not limit, especially it is possible to make spent glycol To improve dispersion stabilization.Additionally, in order to improve dispersion stabilization in the slurry, the most phosphatic dispersant can be added And surface conditioning agent etc..
Polyester and resin composition according to the present invention can meet in the area of 448 μ m 336 μm, a size of 1.5 μm The number of above defect is the physical property of less than 7.The compositions meeting above-mentioned scope physical property goes for electricity Sub-material stripping film and blooming.
It follows that the method that the polyester film preparing the present invention will be described.
In the present invention, use described polymer blend to prepare polyester film by customary preparation methods, such as, use phase In field, pass, known T-die head prepares non-stretched sheet material by melt extruding, by prepared non-stretched sheet material longitudinal stretching 2 to 7 times, preferably 3 to 5 times, and stretch 2 to 7 times by again horizontal (relative to above-mentioned longitudinal direction) for the sheet material of drawn, preferably 3 to 5 Times, thus prepare polyester film.
Additionally, the thickness of prepared film is 1 to 500 μm, in the case of polyester film has monolayer or several lamination, extremely A few layer is configurable to the polyester film according to the present invention.Such as, preparing spherical SiO 2 grain is added when preparing polyester resin Son, or previously prepared polyester resin is mutually mixed with preparing spherical SiO 2 particles, and will wherein contain added particle Resin and be suitably mutually mixed without the polyester resin of particle and make film molding, thus prepare and there is low roughness and height is saturating The polyester film of lightness.
Additionally, in the film with monolayer or several lamination, comprise at least one surface layer (outermost layer) is spherical Silicon dioxide granule can be 0.001 to 0.3wt% relative to the content of polyester resin.
Hereinafter, it will thus provide embodiment is to be more fully described the present invention.But, the invention is not limited in following reality Execute example.
Physical property is measured by following measuring method.
1) sphericity of particle and full-size
Minimum diameter (the P of particlemin) and maximum gauge (Pmax) scanning electron microscope (SEM) of this particle can be used Photo is measured, and therefore, measures minimum diameter and the maximum gauge of 20 particles respectively, and by calculating maximum gauge (Pmax) Divided by minimum diameter (Pmin) meansigma methods determine sphericity.Additionally, calculate the circle of any three points relative to maximum gauge The meansigma methods of round angle.
2) granularity in slurry
Granularity d90 in slurry and dmaxUse the laser light scattering diffraction type grain manufactured by Beckman-Coulter Inc. Degree Distribution Analyzer (model LS1300) is measured.
3) number of internal flaw
The polyester and resin composition making granule is cut into slices melted on microscope slide and prepares the sample that thickness is 500 μm, In transmission light, the defect in the layer that the degree of depth is 180 μm is observed by the optical microscope of 200 amplifications, and by altogether 5 The average opening microphotograph calculates the number that area inside dimension is 1.5 μm disadvantages described above in 448 μ m 336 μm.This Outward, the size of defect is major axis based on this defect, is measured by microscope scale.
4) melted resistance
For pinning performance, melted resistance is measured.To this end, the section of 0.5g polyester and resin composition is placed on In the framework being made up of politef, aluminum electrode is connected to the upper and lower of this section and prepares sample.By described Sample after melted 5 minutes, applies the pressure of 0.7 to 1.0mPa to it, and measured resistance value after 13 minutes at 285 DEG C.When When resistance value is 2 to 8 (× M Ω), polyester and resin composition section can be used for preparing the technique of film.
5) mist degree
By polyester resin standby for the tentative film shaping mechanism of use by extrusion T die melt and by casting drum cooling Prepare the sheet material that thickness is 1690 μm, and along both horizontally and vertically stretching 3 times prepared by prepared sheet material thickness is 188 The sheet material of μm.Then, the mist degree of the film prepared by measurement.
Measure mist degree based on ASTM D-1003 standard, two side parts of the film from above-mentioned preparation are randomly drawed 7 parts and 1 core of this film each cut into the size of 5cm × 5cm, and put into haze meter (Nippon Denshoku NDH 300A) in.Then, the light transmission film making wavelength be 555nm, by using equation below to calculate mist Degree, and calculate its meansigma methods in addition to maximum/minimum.
Mist degree (%)=(total scattered light/total transmission light) × 100%
6) film surface roughness
Based on JIS B0601 polyester film cut into a left side/in/right side 3 part after, more every part is cut into 3cm The size of × 3cm.Then, the surface roughness measuring instrument of Japan Kosaka Laboratory is used, at following measurement bar Measure the two-dimensional surface roughness at least five film surfaces, place under part, and assess average surface roughness Ra (nm).
R a = 1 L ∫ 0 L | f ( x ) | dx
(L: measure length)
Speed: 0.05mm/s
Sampling (cut off): 0.08mm
Measure length (L): 1.50mm
7) navigability (coefficient of friction) of film is measured
The navigability of film represents with coefficient of friction, and coefficient of friction is measured by ASTM D-1894.Described measurement is 23 Carrying out at the temperature of ± 1 DEG C and the humidity of 50 ± 5%RH, used in it, the size of sample is wide 100mm, long 200mm, stretching Speed is 200mm/min.
8) beauty defect (flash of light foreign substance and floating cloud and mist)
After the sample that prepared film is made the preliminary dimension that width is 20cm and a length of 20cm, by three wavelength lamps It is radiated on sample and reflects on the surface of the film, feeling that the Material Definitions of flash of light is for flash of light foreign substance by every kind with naked eyes.This Outward, by three wavelength light irradiation transmissions on sample and on film, and feel fuzzy by every kind with naked eyes and bury at film whole Material Definitions on surface is cloud and mist, measures its degree.
1. ◎ (the most excellent): flashless and cloud and mist.
2. zero (excellent): a small amount of flash of light and cloud and mist.
3. △ (commonly): a large amount of flashes of light and cloud and mist.
4. × (poor): be full of flash of light and cloud and mist on the whole surface.
[embodiment 1]
Relative to the dimethyl terephthalate (DMT) of 100 weight portions, the ethylene glycol of 50 weight portions, 400ppm are followed closely as electrostatic Prick the magnesium acetate of agent and 130ppm to join in esterifier as the antimony trioxide of catalyst, and at 1.5kg/cm2Pressure Heating at a temperature of power and 255 DEG C and discharge methanol, then carry out ester-interchange method 4 hours, thus prepare bis-beta-hydroxyethyl base ethyl pair Phthalic acid ester (BHET, bis-β-hydroxyethyl terephthalate) is as prepolymer.Separated anti-by distillation column The methanol that should generate, after esterification terminates, the ethylene glycol added separates also by distillation column.
Here, as shown in Table 1 below, based on prepared BHET, by the dispersed particle d90 of 0.06wt% be 0.70 μm and The preparing spherical SiO 2 particles (solid content 20wt%) being coated with the metallic compound (aluminium oxide) that thickness is 0.1 μm joins second In glycol, it is added thereto to the 200ppm trimethyl phosphate as heat stabilizer, and temperature is slowly raised 285 by 240 DEG C DEG C, under the fine vacuum of 0.3 torr, then carry out copolyreaction 4 hours, thus prepare intrinsic viscosity (IV) be 0.650 poly-to benzene Naphthalate (PET) resin.
The PET without particle of the PET containing particle and 95% of the above-mentioned preparation of 5% is blended, and passes through extruder Melt extruding, the casting drum then using surface temperature to be 20 DEG C quickly cools down and solidifies, and thus preparing thickness is 2000 μm Sheet material.PET sheet prepared by 110 μm longitudinally (MD) is stretched 3.5 times and at room temperature cools down.Then, by this sheet material 140 Preheat at DEG C, be subsequently dried, and laterally (TD) stretches 3.5 times.It follows that this sheet material to be carried out heat treatment at 235 DEG C, and will The vertical and horizontal stretching at 200 DEG C of thermally treated sheet material 10% carries out heat fixation, and thus preparing thickness is 188 μm and Particle content in telolemma is the Biaxially oriented film of 30ppm.Measure its physical property and be shown in table 2 below.
[embodiment 2]
As shown in Table 1 below, the polyester film of embodiment 2 is prepared in the same manner as in Example 1, and difference is, Use granularity and metal compound coatings thickness and those the different silicon dioxide granules in embodiment 1, and change institute Particle content in the film of preparation.Measure the physical property of the film of embodiment 2 and be shown in table 2 below.
[embodiment 3]
As shown in Table 1 below, the polyester film of embodiment 3 is prepared with method same as in Example 2, and difference is, Change the particle content in film.Measure the physical property of the film of embodiment 3 and be shown in table 2 below.
[embodiment 4]
As shown in Table 1 below, the polyester film of embodiment 4 is prepared in the same manner as in Example 1, and difference is, Use granularity and metal compound coatings thickness and those the different silicon dioxide granules in embodiment 1, and change film In particle content.Measure the physical property of the film of embodiment 4 and be shown in table 2 below.
[comparative example 1]
As shown in Table 1 below, the polyester film of comparative example 1 is prepared in the same manner as in Example 1, and difference is, Use and aspherical but the silicon dioxide granule of calcine type silicon dioxide (SY310, Fuji Silysia).Measure comparative example 1 The physical property of film and be shown in table 2 below.
[comparative example 2]
As shown in Table 1 below, the polyester film of comparative example 2 is prepared in the same manner as in Example 1, and difference is, Use following silicon dioxide granule, wherein, by carry out including by comparative example 1 uses calcine type silicon dioxide (SY310, Fuji Silysia) grind then classification the post processing of 5 μm filtration, the particle mean size of this silicon dioxide granule is adjusted Joint.Measure the physical property of the film of comparative example 2 and be shown in table 2 below.
[comparative example 3]
As shown in Table 1 below, the polyester film of comparative example 3 is prepared in the same manner as in Example 1, and difference is, Change the content of particle used in the comparative example 2 comprised in polyester film.Measure the physical property of the film of comparative example 3 and show In table 2 below.
[comparative example 4]
As shown in Table 1 below, the polyester film of comparative example 4 is prepared in the same manner as in Example 1, and difference is, The particle used not preparing spherical SiO 2 but calcium carbonate (Maruo, KM-30), and change the particle content in film. Measure the physical property of the film of comparative example 4 and be shown in table 2 below.
[comparative example 5]
As shown in Table 1 below, the polyester film of comparative example 5 is prepared in the same manner as in Example 1, and difference is, Change the content of particle used in the comparative example 4 comprised in polyester film.Measure the physical property of the film of comparative example 5 and show In table 2 below.
[comparative example 6]
As shown in Table 1 below, the polyester film of comparative example 6 is prepared in the same manner as in Example 1, and difference is, Preparing spherical SiO 2 particles has the surface of uncoated.Measure the physical property of the film of comparative example 6 and be shown in table 2 below.
[comparative example 7]
As shown in Table 1 below, the polyester film of comparative example 7 is prepared in the same manner as in Example 1, and difference is, Change the content comprising preparing spherical SiO 2 particles in film.Measure the physical property of the film of comparative example 7 and be shown in table 2 below.
[comparative example 8]
As shown in Table 1 below, the polyester film of comparative example 8 is prepared in the same manner as in Example 1, and difference is, Change catalyst, electrostatic pinning agent and the content of phosphorus compound used in the preparation of polyester resin respectively.Measurement is compared The physical property of the film of example 8 is also shown in table 2 below.
By above-mentioned physical property measurement method in above-described embodiment and comparative example preparation polyester and resin composition and The physical property of polyester film measures, and the results are shown in table 1 below.
[table 1]
[table 2]
It is appreciated that compared with comparative example 1 to 7 by upper table 2, in embodiment 1 to 4, catalyst and electrostatic pinning agent Total metal content (MeC+MeP) less than 300ppm, the phosphorus content of phosphorus compound is less than 60pm, and in film containing 0.001 to The preparing spherical SiO 2 particles being coated with metallic compound of 0.3wt%, so that internal flaw and surface defect significantly subtract Few.
Additionally, due to employ the preparing spherical SiO 2 particles being coated with metallic compound, therefore also reduce mist degree with Keep high transparent, and, surface roughness is relatively low and coefficient of friction is moderate, has processing characteristics and the flatness of excellence.
It addition, in comparative example 1 to 5, the particle added does not has spherical form, and does not have and can be defined as tool The structure of shape, therefore cannot measure sphericity, thus also cannot measure the angle of circumference relative to maximum gauge.Therefore, may be used To understand, in comparative example 1 to 5, the particle added aspherical so that internal flaw and surface defect dramatically increase, and And mist degree and surface roughness also increase, this be unsuitable for for need low roughness and the high grade of transparency electronic material stripping film and The polyester and resin composition of blooming.
Furthermore, it is to be understood that in comparative example 6, owing to employing the particle of uncoated metallic compound, therefore with resin The compatibility decline, even if thus still making transparency significantly reduce containing a small amount of particle；And in comparative example 7, owing to making With the preparing spherical SiO 2 particles being coated with metallic compound of excess, therefore the transparency declines, and surface roughness increases, and Surface defect increases.
Furthermore, it is to be understood that in comparative example 8, close owing to being excessively used catalyst, electrostatic pinning agent and phosphatization respectively Thing, the defect counts during therefore metal deposit causes polyester resin increases, and due to the increase of defect so that on film surface Defect significantly increases, and mist degree and surface roughness also increase.
Therefore, the present invention can provide following film, in this film, and the catalyst containing optimum content, electrostatic pinning agent And phosphorus compound, the silicon dioxide granule being coated with metallic compound has suitable granularity, suitable content and suitable gold Belonging to compound coat thickness, so that inside or surface defect substantially reduce, flatness and processing navigability are excellent, film Mist degree is relatively low, and the transparency is excellent.The present invention may be provided for preparing the polyester and resin composition of described film, and preparation should The method of film.

Claims (11)

1. a polyester and resin composition, comprises:
Polyester resin, it is coated with the silicon dioxide granule of metallic compound, catalyst, electrostatic pinning agent and phosphorus compound,
Wherein, described silicon dioxide granule meets Equation 1 below, and any three points of this silicon dioxide granule relative to PmaxAngle of circumference be 85 to 90 degree:
0.9≤Pmin/Pmax≤ 1.0 [equatioies 1]
In equation 1, PminFor the minimum diameter of described silicon dioxide granule, PmaxFor the maximum gauge of this silicon dioxide granule,
Described catalyst, electrostatic pinning agent and phosphorus compound meet equation 2 below to 5:
50≤MeC≤ 200 [equatioies 2]
30≤MeP≤ 200 [equatioies 3]
100≤MeC+MeP≤ 300 [equatioies 4]
30≤P≤100 [equation 5]
In equation 2, MeCFor the metal that contains in described catalyst relative to the content of total polyester and resin composition, at equation In 3, MePFor the metal that contains in described electrostatic pinning agent relative to the content of total polyester and resin composition, in equation 4, MeC+MePFor the metal of described catalyst and electrostatic pinning agent relative to the total content of total polyester and resin composition, at equation 5 In, P is the phosphorus that contains in the phosphorus compound content relative to total polyester and resin composition, and wherein, described content is in terms of ppm.
Polyester and resin composition the most according to claim 1, wherein, described in be coated with the silicon dioxide grain of metallic compound The particle mean size of son is 0.1 to 1.0 μm, and the coating thickness of described metallic compound is 0.01 to 0.1 μm.
Polyester and resin composition the most according to claim 1, wherein, described in be coated with the silicon dioxide grain of metallic compound Son content in this polyester and resin composition is 0.001 to 0.3wt%.
Polyester and resin composition the most according to claim 1, wherein, described in be coated with the silicon dioxide grain of metallic compound 90% cumulative particle sizes (d90) of son is 0.3 to 0.8 μm, maximum particle size (dmax) it is 0.4 to 1.0 μm.
Polyester and resin composition the most according to claim 1, wherein, described metallic compound is selected from aluminium oxide, oxidation Zirconium, titanium dioxide, stannum oxide and zinc oxide any one or two or more.
Polyester and resin composition the most according to any one of claim 1 to 5, wherein, at the area of 448 μ m 336 μm In, the number of defects more than a size of 1.5 μm is less than 7.
7. a polyester film, this polyester film by using the polyester and resin composition described in claim 6, then melt extrude and Prepared by stretching.
Polyester film the most according to claim 7, wherein, what this polyester film contained 0.001 to 0.3wt% is coated with metallization The silicon dioxide granule of compound.
Polyester film the most according to claim 7, wherein, this polyester film has the mist degree less than 5% and the table less than 15nm Surface roughness (Ra).
10. the method preparing polyester and resin composition described in claim 1, including:
When synthesizing polyester resin, mixing is coated with the silicon dioxide granule of metallic compound,
Wherein, described silicon dioxide granule meets Equation 1 below, and any three points of this silicon dioxide granule relative to PmaxAngle of circumference be 85 to 90 degree:
0.9≤Pmin/Pmax≤ 1.0 [equatioies 1]
In equation 1, PminFor the minimum diameter of described silicon dioxide granule, PmaxMaximum gauge for this silicon dioxide granule.
11. methods according to claim 10, wherein, when mixing silicon dioxide granule, are coated with metallization by described The silicon dioxide granule of compound is dispersed in glycol and is mixed into slurry form.
CN201380045267.6A 2012-06-29 2013-06-28 Polyester and resin composition and the polyester film of use said composition Active CN104583314B (en)

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